Scribd
Upload
7 views

Analytical-Complexation

The document discusses the analysis of cations through complexation and precipitation reactions, highlighting the role of ligands in forming coordination compounds with metal ions. It covers various titration methods, including complexometric and precipitation titrations, and emphasizes the importance of formation constants and pH in these processes. Additionally, it addresses the determination of water hardness and the impact of cations on water quality.

Uploaded by

Karen Jane B. Lemosnero
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
7 views

Analytical-Complexation

The document discusses the analysis of cations through complexation and precipitation reactions, highlighting the role of ligands in forming coordination compounds with metal ions. It covers various titration methods, including complexometric and precipitation titrations, and emphasizes the importance of formation constants and pH in these processes. Additionally, it addresses the determination of water hardness and the impact of cations on water quality.

Uploaded by

Karen Jane B. Lemosnero
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd
You are on page 1/ 14

Complexation and Precipitation Reactions and Titrations

How do we analyze cations?


Most metal ions react with electron-pair donors to form coordination compounds or complexes.
The donor species, or ligand, must have at least one pair of unshared electrons available for
bond formation. Water, ammonia, and halide ions are common inorganic ligands. In fact most
metal ions in aqueous solution actually exist as aquo complexes.

Cu2+ as Cu(H2O)42+

A ligand is an ion or a molecule that


forms a covalent bond with a cation
or a neutral metal atom by donating a
pair of electrons, which are then shared
by the two.
Chelate is pronounced kee’late and is
derived from the Greek word for claw.
Dentate comes from the Latin word
dentatus and means having toothlike
projections.
Coordinate covalent bond exists between a metal and a ligand

The selectivity of a ligand for


one metal ion over another refers
to the stability of the complexes
formed. The higher the formation
constant of the metal-ligand
complex, the better the selectivity
of the ligand for the metal relative
to similar complexes formed with
other metals.

The formation of complexes

Complexation equilibria

Unidentate ligands invariably add in a series of steps as shown above. With multidentate
ligands, the maximum coordination number of the cation may be satisfied
with only one or a few added ligands.

Cu(NH3)2+, Cu(NH3)22+, Cu(NH3)32+, and Cu(NH3)42+

Formation constants
Alpha values

(See feature 17-11 for the derivation of the 𝛼 values)

The formation of insoluble species

Ag+ + Cl- → AgCl (s)


AgCl + Cl- → AgCl2- (aq)
AgCl2- + Cl- → AgCl3- (aq)

BiI3 (s)
Ksp =[Bi3+][I-]3

Titration with inorganic complexing agents

Complexation titration

Titration curves for complexometric titrations. Titration of 60.0 mL of a solution that is 0.020 M in metal M
with (A) a 0.020 M solution of the tetradentate ligand D to give MD as the product; (B) a 0.040 M solution
of the bidentate ligand B to give MB2; and (C) a 0.080 M solution of the unidentate ligand A to give MA4.
The overall formation constant for each product is 10 .20

• Tetradentate or hexadentate ligands are more satisfactory as titrants than ligands with fewer
donor groups because their reactions with cations are more complete and because they tend to
form 1:1 complexes.
Precipitation titration

The Shapes of Titration Curves


Titration curve for (A), 50.00 mL of 0.05000 M NaCl titrated with 0.1000 M AgNO3, and (B),
50.00 mL of 0.00500 M NaCl titrated with 0.01000 M AgNO3. Note the increased sharpness of the break
at the end point with the more concentrated solution.
Organic complexing agents

Sodium calcium edetate


• Solutions of EDTA are particularly valuable as titrants because the EDTA combines
with metal ions in a 1:1 ratio regardless of the charge on the cation. For example, the
silver and aluminum complexes are formed by
Structure of a metal/EDTA complex. Note that EDTA behaves here as a hexadentate ligand in that six
donor atoms are involved in bonding the divalent metal cation.

Effect of formation constant


• Complexes with large formation constants, Kf, will be formed faster and more completely.
Effect of pH
• Complex formation is affected by pH because EDTA has multiple acidic and basic
groups
• Titration curve is affected by pH
Minimum pH requirement for successful complexometric titration
of cations using EDTA

The Effect of Other Complexing Agents on EDTA Titration Curves


• Many cations form hydrous oxide precipitates (hydroxides, oxides, or oxyhydroxides)
when the pH is raised to the level required for their successful titration with EDTA.
• Often, auxiliary complexing agents must be used in EDTA titrations to prevent
precipitation of the analyte as a hydrous oxide. Such reagents cause the end points to
be less sharp.

• Ammonia is an auxiliary complexing agent in the equation above


Influence of ammonia concentration on the end point for the titration of 50.0 mL of 0.00500 M Zn .
2+

Solutions buffered to pH 9.00. The shaded region shows the transition range for Eriochrome Black T.
Note that ammonia decreases the change in pZn in the equivalence-point region.

Titration Indicators

Eriochrome Black T (EBT) Calmagite

Transition equilibria for EBT

Titration Methods Involving EDTA


Direct Titration
• Methods Based on indicators for the Analyte
• Methods Based on indicators for an Added metal ion
• Potentiometric methods
• Spectrophotometric methods
Back-Titration Methods
• Involve addition of excess standard reagent mainly to allow sufficient time for the
reaction to take place
• Excess reagent is back-titrated to equivalence point

Displacement Methods

The Scope of EDTA Titrations


• Virtually all cations except alkali metal ions
• Selectivity can be achieved by controlling the parameters (e.g., pH)
o Fe2+ vs Fe3+ (only Fe3+ is analyzed at low pH = 1)
• Thermodynamic properties of the complex can be used (e.g., Ksp , Kf)
• Using masking agents

Masking agent
• a complexing agent that reacts selectively with a component in a solution to prevent that
component from interfering in a determination.
• an auxiliary ligand that preferentially forms highly stable complexes with the potential
interfering ion
• e.g., CN-
Masking and Demasking EDTA titration

Lead, magnesium, and zinc can be determined in a single sample by two titrations with standard EDTA
and one titration with standard Mg2+. The sample is first treated with an excess of NaCN, which masks
Zn2+ and prevents it from reacting with EDTA:

Zn2+ + 4CN- ↔ Zn(CN)42-


The Pb2+ and Mg2+ are then titrated with standard EDTA. After the equivalence point has been reached, a
solution of the complexing agent BAL (2-3-dimercapto-1-propanol, CH2SHCHSHCH2OH), which we will
write as R(SH)2, is added to the solution. This bidentate ligand reacts selectively to form a complex with
Pb2+ that is much more stable than PbY2+:

PbY2+ + 2R(SH)2 → Pb(RS)2 + 2H+ + Y4-

The liberated Y4- is then titrated with a standard solution of Mg2+. Finally, the zinc is demasked by adding
formaldehyde:

Zn(CN)42- + 4CH2O + 4H2O → Zn2+ + 4HOCH2CN + 4OH-

The liberated Zn2+ is then titrated with the standard EDTA solution

Determination of Water Hardness


• Historically, water “hardness” was defined in terms of the capacity of cations in the water to
replace the sodium or potassium ions in soaps and form sparingly soluble products that cause
“scum” in the sink or bathtub. Most multiply charged cations share this undesirable property.
• In natural waters, however, the concentrations of calcium and magnesium ions generally far
exceed those of any other metal ion.
• Consequently, hardness is now expressed in terms of the concentration of calcium
carbonate that is equivalent to the total concentration of all the multivalent cations in the
sample.
• The determination of hardness is a useful analytical test that provides a measure of the
quality of water for household and industrial uses.
• The test is important to industry because hard water, on being heated, precipitates calcium
carbonate, which clogs boilers and pipes.

You might also like